The centennial of the first X-ray crystal structures

A short account is given of the discoveries of the first crystal structures using X-ray diffraction by William Henry Bragg and William Lawrence Bragg, a father and son team working at Leeds University and Cambridge University. Their first publications, separately and together, are highlighted. This is a contribution to the centennial celebrations of these discoveries and looking towards the International Year of Crystallography to be celebrated in 2014 led by the International Union of Crystallography.     

Modulated Structures Induced by Phase Transformations

Abstract

Modulated structures can be found in organic, inorganic and even quasicrystalline structures. They are generally detected by diffraction from the presence of satellites surrounding the Bragg reflections. Their positions may vary continuously with temperature or pressure so that the phase can be considered as incommensurately modulated. Incommensurate phases usually transform to a periodic high symmetry phase by increasing temperature and to a commensurate lock-in phase by lowering the temperature. Their domain of stability varies with temperature, pressure and with the type of compound. Examples have been identified where the interval of equilibrium vary from a few tenths to a few hundreds of degrees. Recent progress in the field of incommensurate structure analysis has been greatly favoured by the superspace group approach which is now almost exclusively applied. In many cases, the resolution of the modulated phases by diffraction methods has contributed towards the understanding of the phase changes. In addition, microscopic models for the transition mechanisms have been developed to understand small organic systems. The methods of molecular dynamics have been able to explain the formation of various sequences of commensurate and incommensurate phases observed experimentally.     

螺旋选晶器对单晶高温合金晶粒取向的影响(英文)

对于航天推进和发电燃气轮机,为了实现更高的效率和性能并同时降低成本和排放,需要发展先进的镍基单晶高温合金。随着合金的发展,合金的铸造技术已经从定向凝固(DS)发展到单晶(SX)。单晶取向与择优取向的偏差已经成为单晶高温合金最重要的铸造缺陷之一。在自行设计的高温度梯度定向凝固装置中,采用改进的Bridgeman法,用螺旋选晶器拉制出DZ417G合金的单晶。使用XRD和EBSD对其取向进行分析研究。结果表明:较小角度的螺旋选晶器可以有效地减少单晶取向与择优取向的偏差。     

Two polymorphs of Ba3Sn2P4: Single crystal and electronic structures

Two polymorphs (I and II) of Ba₃Sn₂P₄ have been found in the same preparative batch. Both compounds crystallize in the centrosymmetric monoclinic space group P2₁/c (#14, a = 7.8669(2) Å, b = 19.2378(5) Å, c = 7.8472(2) Å, β = 112.77(1)°, V = 1095.06(5) Å³, Z = 4, and R/wR = 0.0303/0.0710 for I; a = 7.8771(3) Å, b = 19.4099(7) Å, c = 7.7040(3) Å, β = 112.44(1)°, V = 1088.67(7) Å³, Z = 4, and R/wR = 0.0224/0.0415 for II). Both structures consist of one-dimensional chains separated by Ba²⁺ cations. The isolated chain consists of condensed ethane-like [Sn₂P₆] units. In polymorphs I and II, the condensation and connectivity of the [Sn₂P₆] units are quite different. While [Sn₂P₆] units form four- and six-membered rings in I, they form the five-membered rings in II. The electronic structure calculations indicate that semiconducting behavior is expected for both compounds.     

Characterizing pathological imperfections in macromolecular crystals: lattice disorders and modulations

Macromolecular crystal structure determination can be complicated or brought to a halt by crystal imperfections. These issues motivated us to write up what we affectionately call ‘The Definitive Hitchhiker’s Guide to Pathological Macromolecular Crystals: Lattice Disorders and Modulations’. Perhaps the most challenging imperfections are lattice order–disorder phenomena and positional modulations. Many of these types of crystals have been solved, and progress has been made on the more challenging forms. Diagnostic tools and how to solve many of these problem crystal structures are reviewed. New avenues are provided for approaching the solution of incommensurately modulated crystals. There are a good number of case studies in the literature of lattice order–disorder phenomena and crystallographic modulations that make it timely to write a review. This review concludes with a projected pathway for solving incommensurately modulated crystals, personal views of future directions and needs of the crystallographic community.     

原始组织对高温合金热处理组织和力学性能的影响

对具有不同枝晶间距的CMSX 2单晶高温合金的凝固组织特征及其对热处理组织和持久性能的影响进行了研究。考察了不同温度下不同枝晶间距组织的固溶情况及热处理后的组织均匀性 ,测试了持久性能。结果表明 :随着凝固组织的细化 ,合金的组织均匀性得到提高 ,从而有效提高了合金的固溶温度 ,增大了热处理均匀化效果 ;CMSX 2合金铸态超细组织单晶的持久寿命是粗枝晶单晶的 1.4 5倍 ,热处理态超细枝晶单晶的持久寿命是粗枝晶单晶的 1.85倍。单晶高温合金组织超细化是显著提高合金高温力学性能的有效手段     

What is a crystal to the new chemical crystallographer,after that first,automated structure analysis?

This educational review postulates the importance of maintaining an adequate level of crystallographic education among structure-dependent scientists whose interests are not primarily in crystallography, at a time when automation and validation have made it possible to obtain high-quality structure analyses in many cases with a minimum of crystallographic background. The topics addressed are intended to form a second round of crystallographic education for a novice user whose first round involved hands-on experience with structure solution and an introduction to elementary concepts. The specific topics, chosen for their relevance as basic knowledge and their lack of emphasis in many formal treatments, are (1) crystallographic reference frames and the utility of the reciprocal cell in geometrical calculations; (2) the relationship between the two concepts that constitute our model of the crystal, namely the unit cell and the lattice; (3) the manner in which an atom is represented in concept and in practice; (4) the importance of interleaved symmetry elements required by the presence of additional symmetry on a lattice; (5) the harnessing of the natural properties of the crystalline state for the potential manipulation of properties of synthetic crystals; and (6) useful terminology for navigating a crystal structure.     

The use of partial observations,partial models and partial residuals to improve the least-squares refinement of crystal structures

Some common misconceptions in least-squares crystal structure refinement can be resolved by recasting the usual equations in terms of partial observations, partial models and partial residuals. An observation has components that are determined by an initial calculated model and each component, including the background, is considered to be a partial observation of the total observation. The use of partial observations, partial models and partial residuals allows various misconceptions to be identified and suggests ways to improve the least-squares methodology. A fixed component of a model of peak-plus-background does not fix its contribution to the observation for each refinement step. A covariance matrix obtained from the least-squares equations enables a standard uncertainty to be estimated for any function of the structural parameters. An oversight in current refinement methods is the failure to estimate the variances of components of the calculated model of an observation and the fraction of each residual associated with the various features of a refinement. A distinction should be made between least-squares equations for model development and least-squares equations for the estimation of a variance–covariance matrix. Methods for detecting systematic errors are discussed. A proposed look-ahead option for model development includes the assessment of the ability to refine parameters. For pseudo-symmetric structures, the use of symmetrized combinations of pseudo-equivalent intensities allows the reliability of minor components of the intensities to be better evaluated. It is also shown how homometric structure solutions can result from the use of powder diffraction data or equally twinned crystals.     

晶体取向对镍基单晶合金蠕变行为的影响

通过蠕变曲线测定及组织形貌观察,研究[001]、[011]取向镍基单晶合金在蠕变期间的组织演化及变形特征。结果表明:经完全热处理后,[001]和[011]取向合金中立方γ′相均以共格方式镶嵌在γ基体相中,并沿〈100〉取向规则排列。蠕变期间,[001]取向合金中γ′相沿垂直于应力轴方向形成N-型筏状组织,而[011]取向合金中γ′相沿[001]取向形成纤维状筏形组织,且在(100)晶面的筏状γ′相与施加应力轴方向呈45°角排列,其中,立方γ′相不同晶面中扩张晶格的法线方向是筏状γ′相的生长方向。在试验温度和应力范围内,与[011]取向合金相比,[001]取向合金具有较好的蠕变抗力。在高温蠕变后期,两取向合金中的筏状γ′相均发生粗化和扭折,其中,[001]取向合金在蠕变后期的变形机制是位错剪切γ′相,而[011]取向合金的变形特征主要是形变位错在基体通道中滑移。     

单晶高温合金的选晶行为

对高温合金单晶选晶生长工艺进行了实验研究,揭示了螺旋选晶器和缩颈选晶器的原理,实验结果表明,在螺旋选晶器中,晶体横向拚优生长与螺旋结构的耦合作用,形成连续选晶过程,是螺旋选晶的主要原理,其选晶作用良好;而在缩颈选晶器中,几乎只存在单一的机械阻隔选晶行为,多重缩颈结构对于改善选晶作用并不明显,选晶效果不好。     

Relationship between solid/liquid interface and crystal orientation for pure magnesium solidified in fashion of cellular crystal

The relationship between the solid/liquid interface and the crystal orientation for pure magnesium,which grows in fashion of cellular crystal in unidirectional solidification,was investigated.The results show that the energy of the solid/liquid interface is the lowest during cellular crystal growth of pure magnesium;and the solid/liquid interface is covered by the basal face{0001}and by the crystal face made up of three atoms located at the orientation{0001}<0100>and two atoms located at the inner of magnes...     

High-pressure synthesis and crystal structures of two new polyphosphides, NaP5 and CeP5

Two novel polyphosphides, NaP₅ and CeP₅, were prepared in a BN crucible by the reaction of elemental components under a high pressure of 3 GPa at 800–950 °C. The X-ray structural analysis showed that NaP₅ crystallizes in an orthorhombic space group Pnma with a=10.993(2) Å, b=6.524(1) Å, c=6.903(1) Å, Z=4 and CeP₅ in the monoclinic group P2₁/m with a=4.9143(5) Å, b=9.6226(8) Å, c=5.5152(4) Å, β=104.303(6)°, Z=2. The crystal structure of NaP₅ consists of a three-dimensional framework _∞³[P₅]¹⁻ constructed by P---P bonds among four crystallographically inequivalent phosphorus sites, with large channels hosting the sodium cations, while CeP₅ is a layered compound containing _∞²[P₅]³⁻ polyanionic layers that are separated by Ce³⁺ ions. NaP₅ exhibits the diamagnetic behavior, while the temperature-dependent magnetic susceptibility of CeP₅ essentially follows the Curie–Weiss law.     

不同模组结构高效制备单晶叶片定向凝固过程的温度场及组织模拟

针对18个单晶高温合金叶片高效制备过程中温度场不均匀而导致的杂晶缺陷问题,设计了3种不同的单晶叶片模组结构,采用ProCast软件和CAFE模块对第2代单晶高温合金DD6不同模组结构在高速凝固工艺下的温度场和晶粒组织进行模拟研究,分析了不同模组结构下叶片的温度场演化和抽拉速率对杂晶的影响。结果表明,单层模组由于中柱的保温作用较小,导致叶片近中柱侧的散热效率高于近炉壁侧,凝固过程固液界面弯曲严重,凝固过冷大,杂晶形成倾向大;通过对单层模组添加套筒,以加强保温作用,可有效改善温度场,减小固液界面弯曲程度,避免杂晶形核;而双层叠加模组温度场分布均匀,凝固过冷小,杂晶形成倾向小。套筒模组和双层叠加模组在抽拉速率小于100μm/s时均无杂晶形成,但双层叠加模组将模组直径缩小为其余2种模组结构的一半,降低了对炉体型腔尺寸的要求,有望实现单晶叶片的高效制备。     

Al63Cu25Mn12准晶形核剂对铸态铝合金显微结构的影响

在纯铝中添加Al63Cu25Mn12准晶熔炼出了Al-Cu-Mn合金,对铸态试样的显微组织和晶体结构进行了研究。结果表明,铸态共晶组织包含Al和在Al2Cu相基础上形成的新相,其中共晶相中的Al晶粒的取向与相邻Al基体接近。共晶组织中的另外一个新相是在共晶Al相形成网格后才在其网格内结晶形成,其电子衍射花样特点表明,这个相是在无序Al2Cu相的基础上,沿（1-10）面2倍周期有序形成的一种新相。     

取向匹配性对DD6单晶接头持久性能的影响

对4种不同晶体取向组合的DD6单晶试样进行了TLP扩散焊,包括连接面垂直或平行于单晶生长方向,二连接试样取自同一单晶试样且二者的晶体取向完全匹配或二连接试样取自不同单晶试样即二者的晶体取向有一定差别,并测试了接头持久性能.结果表明,连接试样的晶体取向对接头持久性能影响不明显,但其匹配性对接头持久性能有较大影响.当二连接...     

NDT of shape adaptive structures

Health monitoring of smart structures is important for maintaining their performance. Damage may be caused by electrical or mechanical overload, or by ageing. We indicate methods that allow the detection and characterisation of defects in a non-destructive way: impedance spectroscopy, dynamic thermography and interferometry. Examples are shown for a model sample and an industrial structure.     

晶体取向对镍基单晶高温合金铸态组织和偏析的影响

用光学显微镜观察了沿 [0 0 1],[0 11]和 [111]方向生长的镍基单晶高温合金的枝晶形态。结果表明 ,以枝晶界面生长的单晶中生长方向完全由择优取向〈0 0 1〉决定 ,[0 0 1]方向中形成平行于轴向的枝晶 ,[0 11]和 [111]方向中由于不同取向的枝晶交错生长 ,形成多种位向的亚晶界。在垂直于枝晶方向的 { 0 0 1}面内测定的一次枝晶间距 ,按 [0 0 1]→ [0 11]→ [111]次序增大。用电子探针测定了不同取向中合金元素的偏析比 ,Al,Co ,W的偏析情况不受晶体取向影响 ,Ti和Cr的偏析比按 [0 0 1]→ [0 11]→ [111]的顺序减小 ,Ta和Mo的偏析程度无确切变化规律。各元素在不同取向中偏析的变化是由元素的扩散能力和枝晶空间构形共同决定的。     

单晶UBM在电子封装微互连中的研究进展

3D封装是未来电子封装制造技术领域的重要发展方向,3D封装中微凸点的尺寸将急剧降低,此时,芯片凸点下金属层(UBM)可能仅包含几个甚至单个晶粒。因此,UBM的晶体取向对界面金属间化合物(IMC)的形核和生长过程将具有显著影响,而界面IMC的特性会直接影响到凸点微/纳尺度互连的可靠性。因此,以单晶作为UBM研究界面物质的传输与IMC的生长规律,具有重要的理论和应用价值。本文对近年来以单晶Cu、Ni和Ag作为UBM焊点的界面反应进行综合分析,总结了单晶UBM上特殊形貌IMC晶粒的形成条件、界面IMC与单晶基体的位向关系、IMC的生长动力学过程、柯肯达尔空洞的形成规律、单晶UBM上IMC的晶体取向调控方法及晶体取向对无铅焊点力学性能和可靠性的影响,为评价单晶UBM凸点的力学性能和可靠性及提供指导。     

晶片材料的超精密加工技术现状

文章介绍了晶片材料的超精密加工设备以及几种典型晶片材料加工工艺的最新发展 ,综述了几种典型超精密加工设备的特点以及单晶硅片、石英晶体、K9玻璃、钽酸锂单晶材料的加工工艺方法 ,探讨了晶片材料的超精密加工技术的发展趋势。     

Smart structures assembly through incremental forming

Smart structures are becoming more and more important in the transport and building sectors. Today, the components of the structures are generally produced separately and assembled in additional processes afterwards. An alternative approach, which combines the forming of metallic parts and the assembly of the structures in one process step, is proposed in this paper. Incremental forming processes are applied for this operation. Significant joining mechanisms will be analyzed and some applications of this combined forming and assembly process are shown.